Improved cobalt molybdate catalyst for oxidizing olefins



United States Patent M U.S. Cl. 252-439 6 Claims ABSTRACT OF THE DISCLOSURE This is a division of application Ser. No. 340,506 filed Ian. 27, 1964, and now abandoned.

This invention relates to a method for producing a mixture of acrolein and acrylic acid by the vapor phase oxidation of propylene and to a catalyst containing CoMoO TeO and a rhenium compound for effecting the conversion of propylene to the said products.

Vapor phase oxidation of propylene to acrolein is well known in the art, but the known processes have at least one of the following shortcomings, either conversion of propylene to useful products per pass is quite low, which necessitates a separation and recycling step, or the product of oxidation is almost exclusively acrolein which has some industrial utility, but not in the volume attained by acrylic acid. Acrylic acids can be produced from acrolein, but yields are not good or the reaction time is exceedingly long. These additional steps for producing acrylic acid from acrolein make the process for acrylic acid production economically unattractive.

With the catalyst of this invention it is possible to convert from about 68 to 100% of the propylene per pass and obtain yields of about 50 to 88% of desired products. The ratio of acrylic acid to acrolein (i.e. the mol percent yield of acrylic acid, based on propylene converted) can vary considerably and can be as high as about 13 to l or as low as about 1 to 2, depending in part on catalyst composition and in part on reaction conditions. This flexibility is desirable, as it provides a means for limiting the production of one of the undesired end products.

The temperature at which the conversion of propylene to acrolein and acrylic acid takes place with the catalyst of this invention can vary between about 300 and 425 C. Above 425 C., there is an excessive decomposition of the partially oxidized olefinic products to CO and C0. The most desirable operating range, however, is from about 350 to 400 C.

The reaction can be carried out with either a fixed bed or fluid bed catalyst system. The catalyst can be supported or unsupported. Certain supports, such as silica gel or pumice appear to act as catalyst diluents which tend to lower conversion of propylene and form lower yields of acrylic acid. This dilution effect is not as pronounced with diatomaceous earth supports. It is preferred to use an unsupported catalyst.

The molar ratio of components in the catalyst can vary as follows:

3,451,946 Patented June 24, 1969 With large amounts of Te0 there is a tendency to favor production of acrolein and a reduction in the amount of acrylic acid.

PREPARATION OF CATALYST One mol (291 g.) of cobaltous nitrate was dissolved in 300 g. of water. A solution of 1 molar equivalent of ammonium molybdate (177 g.

was prepared by heating and stirring in 200 ml. of water, and thereafter cooled.

The cobaltous nitrate solution was added, with constant stirring, to the ammonium molybdate solution. A solution of g. concentrated NH.,OH in 80 g. of water was added dropwise to the cobaltous nitrate-ammonium molybdate mixture. Stirring was continued for 30 minutes after addition of the NH OH. The slurry was filtered and washed with 1500 ml. water. The solids were resuspended in water two additional times and filtered. The solids were washed with 1500 ml. water each time they were filtered. To the cobalt molybdate are added various quantities of TeO and HReO, as fine powders and dispersed as evenly as possible by stirring. The amount of TeO and HReO will vary depending on the ratio of or R 0 desired in the completed catalyst. For preparing a molar ratio of 800 CoMoO 30 Te0 and 1 HReO, the amount of TeO- needed is 3.2 g. and the amount of perrhenic acid is .250 g. or its equivalent as the ammonium salt. At this stage the catalyst is in the form of a paste. This is dried in a vacuum oven at 80 C. and then baked in an oven at 400 C. for 16 hours. The catalyst is then ground to the desired size. For fixed bed systems a 10-18 U.S. sieve size is satisfactory. For fluid bed systems operating at atmospheric pressure or slightly above, particles passing an 80 mesh U.S. sieve size screen but not a 325 mesh are most desirable.

For preparing a supported catalyst the most desirable procedure is to prepare a solution of the cobaltous salt in water, dissolve ammonium molybdate in water and dissolve ammonium tellurite in HNO solution while maintaining the pH of the latter at 4-6, and a solution of HReO is prepared in Water. The cobaltous salt is added to the molybdate solution. Then the tellurite solution is added, and the solution of perrhenic acid. Finally silica gel or diatomaceous earth or other carrier of the particle size desired is added to the slurry, the slurry is evacuated, stirred well to distribute the carrier uniformly and thereafter filtered, washed and baked at 400 C. for about 16 hours.

Any soluble or insoluble tellurite which can be converted to Te0 during the catalyst preparation can be used. Similarly any rhenium compound convertible to Re O can be employed.

The preferred catalysts are those in which the molar ratio of cobalt molybdate is about 800, the tellurium oxide is 20-30 and the perrhenic acid is 1-2.

THE REACTANTS The reactants are propylene, either pure or contaminated with propane or other readily volatile hydrocarbons, and oxygen, or an oxygen containing gas, such as air, or a mixture of nitrogen and oxygen containing more than 21% oxygen. For economic reasons air is preferred as the oxidizing reactant.

Hydrocarbons such as ethane, ethylene, propane, butane and the like are not oxidized to any great extent and therefore'can be used as diluents. However, they do use up some oxygen and therefore the quantity of the latter must be adjusted to provide best results.

Because some of the propylene is oxidized to CO and CO it is most desirable to use a stoichiometric excess of 30100% oxygen in the reaction. The preferred excess lyst have a profound efl'ect on conversion and on the tem perature at which conversion is effected. The best data known for this type of reaction are reported in Belgian Patent 587,683 where a catalyst containing CoMoO and TeO but no rhenium shows a conversion of 42% propylis about 66 mol percent excess oxygen. The maximum ene and yields of acrolein of 12% and acrylic acid of 58% amount of oxygen is not determinable, but the mixture on the propylene converted at 450 C. The efiiciency for of olefin and oxygen should be such that it is not exacrolein production is about 5% and for acrylic acid, plosive under the reaction conditions. about 24% for a total efliciency of 29%, as compared Water vapor is a desirable adjunct in the reaction for to a minimum efiiciency of about 59.9% as calculated the reason that higher yields of desired products, acrolein from e d 1n h abov t l In Belglan P tent 2 and acrylic acid, are obtained if it is present, but it is not Where a p l 4 Catalyst COntalnlHg 5 s essential to the obtainment of good yields of products by and the oxldatlon 1s effected at 0.55 atmosphe 4 p pylthis procedure. ene conversion of 81% with a 36% yield of acrylic acid The ratio of water vapor to propylene can range from and 14% acrolein is reported. The combined efiiciency 1s t 7 40.5% at a temperature of 433 C. The examples which tol low are intended to explain the Example 11 invention but not to l1m1t 1t.

In order to determme the effect of water vapor the fol- Example 1 lowing series of runs were made at 350 C. with the catalyst described in Example 1. In all instances the A series of runs was made in a fixed bed reactor, which amount of excess oxygen was 66%, based on the propylconsisted of a high silica glass tube 28 cm. long and 22 ene fed. mm. O.D. containing three inlets, one for air, one for TABLE II propylene and one for steam. The reactor had three sets 25 I 1 t M l of external electrically operated heating coils, one of Water Contact Molpercent l y igiri 611121 5153? wh1ch could heat the entire outer surface of the reactor p i e C e i m A AA and each of the other coils would heat only about one m AA half the length of the reactor. The outlet vapors were 32 33% 1g? 53g 3.8 56.1 passed through a Perkin-Elmer gas chromatograph Model 0 37 97:5; 3 i 1 3 21;; 154D for continuous analysis of exit gases. 0 25 82.7 32. 5 39.3 26.8 32.4

The catalyst (60 ml.), made in a mol ratio of 800 C 0 2 0 and 1 1.111 0 fill d about 90% of the These data show that water 15 beneficial, but not essenvolume f the reactor tial, for obtaining good yields of acrolein and acrylic Gases were preheated to about 250 C. before entering 361d Wlth thfi catalyst The Ylelds P acryllc acid are h reactor somewhat lower and those of acrolein somewhat higher The ratio of air to propylene was adjusted to provide 111 the abence of if exces} 4 Pres?nts about 66% excess over the stoichiometric amount needed Problem In the SepaTatloIl and Purification p The for converting propylene to acrylic acid. amount 01: water can be controlled to some degree by Steam, in a ratio of 1 to 4 mols per mol of propylene, 4o operatlng 1n thlS manner- Was added to the reactor. E am 1 HI Contact time in all fixed bed tests was cold contact X p e time. A 20 second cold contact time is equivalent to about This series of runs was made with a catalyst having 8 seconds hot contact time. :1 mol ratio of 800 CoMoO 15 of TeO and 1 of Data obtained in these runs are tabulated below: HReO The data are tabulated below.

TABLE III M01 Percent M01 Percent Percent Steam! Contact Percent Yield Etficiency excess Propylene Time, Conversion 5 Ratio See. 1., C. Propylene Aer AA Aer. AA

TABLE I M01 Percent Yield on M01 Percent propylene Efiiciency Percent Steam! Contact Percent converted excess propylene Time, Conversion 0] ratio Sec. T.,C. Propylene Acr. AA .Acr AA NOTE .-Acr. =acrol0in; AA=acrylic acid.

These data show that good conversions of propylene are obtainable per pass at temperatures of 320 C., that the ratio of acrolein to acrylic acid can be controlled by controlling either contact time or temperature or both and that at a temperature of 350 C. about 50% or more of desirable products can be obtained on extremely high conversions of propylene. They also point out that ex- 70 was run under conditions of 66% excess oxygen, 4 mols steam per mol of propylene and a 20 second contact time and the yields of acrylic acid were quite low. At 335 C. conversion of propylene was 55%, the yield of acrolein was 20.5% and that of acrylic acid was 19.6%. At

tremely small amounts of rhenium compound in the cata- 355 C. conversion was 80.6%, yield of acrolein was 14.6% and that of acrylic acid was 25.7%; at 385 C. the conversion was 89.1%, the yield of acrolein was 4.5% and that of acrylic acid 20.1%. This shows that the eifect of rhenium compounds in the ratio 0.5 mol is too low to be practical.

Example IV The catalyst in these tests was made by the procedure described above using a ratio of 800:30:1 of molybdate, to tellurium, to rhenium, respectively. The contact time in each instance was 20 seconds. Reaction temperature and oxygen-propylene ratios were varied. The data obtained in these runs are tabulated below.

6 The entire mixture was then placed in a beaker and dried on water bath. Additional drying at 90 C. in a forced draft oven for four hours was given to the catalyst.

It was then baked for 48 hours at 400 C., crushed and 5 sieved. This catalyst had a ratio of 800 mols CoMoO 30 mols TeO, one mol HReO and 400 mols SiO- To the reactor were added 40 g. of the catalyst of -18 mesh size.

In each instance an oxygen excess of 66%, 4 mols of water vapor per mol of propylene were used. The cold contact time was 13 seconds.

The results of these tests are tabulated below:

TABLE IV Yield, M01 M01 Percent Percent E M0] Percent Percent Eificiency excess propylene conversion p" C 0: ratio propylene Aer. AA Acr. AA

With this catalyst the ratio of end products obtained TABLE VI can be varied considerably by ad ustmg the temperature M01 Percent Yield M01 Percent or the amount of excess oxygen. Mol Percent Efficiency Conversion Example V Temp.,C. Propylene Aer AA Aer. AA 355 84. 3 25. 0 57. 0 21. 0 48. 0 The catalyst for these tests contained the following 380 M3 1&0 555 15.0 523 molar ratios of ingredients: cobalt molybdate 800, tel- 400 M3 4L1 M5 m2 lurium oxide 300, HReO, 10. In each case the runs were made with 66% excess oxygen, a ratio of 4 mols of water per mol of propylene and a 20 second contact time. The results of the tests are tabulated below:

TABLE V Mei percent yield on Propylene Mol percent Mol percent Converted Eificiency Temp., Conversion C Propylene Acr. AA Aer. AA

Example VI A supported catalyst was prepared as follows: 349.5 g. of cobaltous nitrate were dissolved in 2 liters of concentrated NH4OH, 212.9 g. of ammonium molybdate was added to the cobaltous nitrate. 8.6 g. of telluric acid and 0.377 g. of HReO were separately dissolved in water and added to the cobaltous nitrate-ammonium molybdate mixture.

Microsperoidal silica (144.0 g.) having a surface area of about 350 m. per gram was added to 600 ml. concentrated ammonium hydroxide and the mixture was heated at 65 C. for three hours. The silica was filtered and allowed to air dry.

The silica was placed in a suction flask and part of the solution containing the remaining ingredients was added. The flask was evacauted to fill the interstices of the silica with catalyst. The procedure was repeated after addition of the remainder of the cobalt nitrate-ammonium molybdate, telluric acid and perrhenic acid mixture.

If colloidal silica in aqueous suspension is used as a support, the preferred way of making the catalyst is to precipitate the ingredients on the silica particles.

Examples VII In these runs the catalyst was composed of a mol ratio of 800 for the cobalt molybdate, 30 for Te0 and 10 for HReO The catalyst was made by the procedure described above and was also used in a mesh size of 1018. In all these runs 66% excess oxygen, and 4 mols of water per mol of propylene were fed into the reactor. The data The following data show results obtained with a catalystof 800 mols cobalt molybdate, mols Te0 and 2 mols HReO The feed contained 66% excess oxygen, 4 mols of steam per mol of propylene and the contact time was 20 seconds.

TAB LE VIII Mol Percent Mol Percent M01 Percent Yield Efficiency Conversion 6 Temp, C. Propylene Aer. AA Acr. AA

7 mesh used in the fixed bed system. Thus, the catalyst was ground more finely and the portion which passed through an 80 mesh U.S. sieve but not through a 325 mesh was used. This range of particles sizes was found to be satisfactory because it could be fluidized fairly uniformly ture was passed into the bottom of the reactor. The volume of air, steam and propylene is controlled through measuring devices, so that ratios of reactants and diluents can be adjusted to the desired levels. Temperature measurements are made in the reactor sections by use of therthrough the bed and did not apepar to striate or form mostats. The effluent from the reactor is run through a channels. It is also desirable in fluid bed systems to have water-cooled condenser and then the vapors from the a catalyst with as low a density as possible, so that it can condenser are passed through two Dry Ice traps to conbe fluidized quite readily and remain so during the entire dense all the vapors of the organic chemicals formed in course of the reaction. For this reason it is preferable to the reaction. The gases which are not condensed are use catalyst supports where possible, so as to present a passed through a gas meter to measure their volume and large catalytic surface area. When silica is used as a supthen through a vapor phase chromatograph to determine port it is preferable to fill as completely as possible the their compositions. void in the silica particles, because free silica surfaces are Data from these runs are recorded below.

TABLE IX M01 Percent Yield on Mol Percent Converted 0 11s Efiiciency C.'l., M01 Percent O2ICaHe Ego/C 110 Sec. T., C. C Hs Converted Aer. AA Aer. AA

2. 4 4. so 8. 4 350 97. e 1e. 2 s3. 1 15.8 51.8 2. 71 4. 58 s. 4 300 5a 7 47. 9 41. 5 27. 2 2a. 5 2.44 5.44 7.3 350 96.4 8.5 56.6 8.3 54.3 2. e5 4. 66 s. 2 s50 89. 5 14. 4 52. s 12. 9 47. s

NorE.-O.T.=hot contact time.

inactive and may even be slight inhibitors of the catalyst. If the silica is porous the cobalt molybdate can be precipitated in an aqueous slurry of the silica or a blend of colloidal silica, such as Ludox, and a microspheroidal silica can be slurried and this then added to a paste of the CoMoO Te0 HReO uniformly dispersed therein, dried, baked, crushed and sized prior to use.

For making fluid bed runs, catalyst to a depth of 6-12 inches was added to a high silica (Vycor) glass reactor about 5 feet long having an CD. of 38 mm. The bottom of the reactor had a sintered glass plate to aid in distributing the gases as they entered the reactor and to retain the catalyst. Water was vaporized and mixed with air, then passed through a heating unit to raise the temperature to about 200-250 C. The air-steam mixture was The condensed liquids are also analyzed for their composition.

The contact time in all of the fluidized catalyst tests is hot contact time, as contrasted with cold contact time reported for all the fixed bed tests.

Example X TABLE X M01 Percent Yield on M01 Percent Converted 03H: Efficiency C.'I., M01 Percent OzICaHs HzO/CaHs Sec. T., C. caHeConverted Acr. AA Aer. AA

blended with propylene just prior to entry of the gases Example XI into the reactor. Volumes of gaseous ingredients were controlled by the uses of rotameters. The reactor was heated electrically to the desired temperature and maintained at such temperature through the use of rheostats.

Example IX In this series, 133 g. of a catalyst of 800 mol CoMo0 30 TeO and 1 HReO were added to the reactor. The catalyst occupied a depth of about 7 inches. Air was preheated to slightly below reaction temperature and fed into the reactor at a pressure just suflicient to obtain good fluidization of the catalyst. The reactor section was also heated electrically to a temperature slightly below that desired for reaction. The water was passed through a vaporizer and blended with the air and the blend was run through the heating unit to raise the temperature of the mixture to the desired temperature. Propylene Was admitted into the heated air-stream and the entire mix- The runs of this example were made with a supported catalyst having a composition equivalent to 800 mols CoMoO 30 mols TeO one mol HReO and a total of 800 mols of silica.

The silica support was prepared by adding 690 mols of microspheroidal silica gel to an aqueous suspension of colloidal silica Ludox LS, containing enough silica to provide 160 mols SiO The mixture of the two silica ingredients was stirred thoroughly in an attempt to fill all the pores in the microspheroidal siilca gel, which had a surface area of about 350 meters per gram. The silica mixture was added to an aqueous paste of the remaining ingredients, mixed by stirring for about a half hour, then dried, baked, crushed and sized.

To fill the reactor to a 12 inch settled height required 177 grams.

Data obtained in these runs are tabulated below.

TABLE XI Mol Percent Yield on Mol Percent Converted CsHa Efficiency C.I., M01 Percent O2/C3He H2O/CaHs Sec. T., C. 0 Converted Aer. AA Aer. AA

If microspheroidal silica is used alone as a support, the catalyst should be prepared by precipitating the CoMoO onto the siilca particles to fill as much of the surface as possible. The tellurium compound and the rhenium compound can be added to the occluded silica before drying and baking.

For comparative purposes the components of the catalyst of this invention were tested for their ability to convert propylene to acrylic acid and acrolein.

TeO alone shows practically no activity below 400 C. At 420 C. only 11% of the propylene fed, using an excess of 66% oxygen and 20 second contact time, was converted, about 90% of the product converted was acrolein.

CoMoO alone showed a conversion of 68.1%, at 370 C. with an excess of 66% oxygen and a 28 second contact time, but the yield of acrolein was only 3.4% and that of acrylic acid 3.5%. Considerable amounts of acetic acid are also produced.

It requires the unique combination of cobalt molybdate, plus the amount of a tellurium compound in the range indicated herein and the amount of a rhenium compound in the range indicated to provide a superior catalyst for producing the products desired from propylene and oxygen.

We claim:

1. A composition comprising on a molar ratio 800 CoMoO 15-300 TeO and 1-10 of HReO 2. A composition comprising on a molar ratio 800 CoMoO 15-30 Te0 and 1-2 HReO 3. A composition comprising on a molar ratio of 800 COMOO4, T602 and 1 HRCO4- 4. A composition comprising on a molar ratio 800 C0MoO o T and 10 HReO 5. The composition of claim 1 impregnated on a silicic support.

6. A composition comprising on a molar ratio 800 CoMoO 15-300 TeO and 1-10 of R6207.

References Cited UNITED STATES PATENTS 3,369,049 2/1968 Eden 260604 3,177,257 3/1965 Detling 260604 3,301,906 1/1967 Besozzi 260604 3,322,693 5/1967 Bethell 252470 PATRICK P. GARVIN, Primary Examiner.

US. Cl. X.R. 260-533, 604

223g UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 451 9'46 Dated June 2 69 Inventor) Charles E Ziegler and Jamal S. Eden It is certified that error appears in the above-identified patent and that said Letters Patent are herebiy corrected as shown below:

[ Column 5 line 65 for "microsperoidal" read --microspneroida1--. Column 5 line 46 for Table VIII" reed --Table VII--; column 6 line 66 for "655" read --355--- Column 7 line 4 for "particles" read --pa.rticle-- column 7 line 6, for "apepar" read --a.ppeer--- column 7 line 65 after "air-" insert --stea.m--. Column 6, Table IX under Mol Percent Efficiency AA, line 3 for "5 4. 3" read --5 L.8--; column 8 Table IX, under Mol Percent Efficiency AA," line for "47. 8'? read --47. 3--; column 8 Table XI under H O/C H line 1, for "9. 98" read --3.98--; column 8 Table )(sulgder M01 Percent Efficiency AA line 2 for "28.6" reed SIGNED AN'D SEALED APR? 1970 (SEAL) Atteat: m m

WILLIAM E- B-QHUY Edwfld member In Comissioner of Pat. ants Attestiug Officer 

